(4bS,8aS)-1-Isopropyl-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octa-hydro-phenan-thren-2-yl acetate.

The hemisynthesis of the title compound, C22H32O2, was carried out through direct acetyl-ation reaction of the naturally occurring diterpene totarol [systematic name: (4bS,8aS)-4b,8,8-trimethyl-1-propan-2-yl-5,6,7,8a,9,10-hexa-hydro-phen-an-thren-2-ol]. The mol-ecule is built up from three fused six membered rings, one saturated and two unsaturated. The central unsaturated ring has a half-chair conformation, whereas the other unsaturated ring displays a chair conformation. The absolute configuration is deduced from the chemical pathway. The value of the Hooft parameter [-0.10 (6)] allowed this absolute configuration to be confirmed.

Related literature

For the synthesis, see: Short & Stromberg (1937 ▶). For biological properties of totarol, see: Barrero et al. (2003 ▶); Bernabeu et al. (2002 ▶); Haraguchi et al. (1996 ▶); Marcos et al. (2003 ▶); Tacon et al. (2012 ▶). For related structures, see: Zeroual et al. (2008 ▶); Pettit et al. (2004 ▶). For structural discussion, see: Cremer & Pople (1975 ▶); Flack (1983 ▶); Flack & Bernardinelli (2000 ▶); Spek (2009 ▶).

Experimental

Crystal data

C22H32O2

M = 328.47

Monoclinic,

a = 7.4250 (2) Å

b = 10.5716 (3) Å

c = 12.0747 (3) Å

β = 90.124 (2)°

V = 947.79 (4) Å3

Z = 2

Cu Kα radiation

μ = 0.55 mm−1

T = 180 K

0.38 × 0.38 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) ▶ T min = 0.860, T max = 1.000

4370 measured reflections

2511 independent reflections

2490 reflections with I > 2σ(I)

R int = 0.012

θmax = 60.7°

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.075

S = 1.04

2511 reflections

225 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Refined as an inversion twin.

Absolute structure parameter: 0.0 (3)

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814002748/xu5767sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002748/xu5767Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002748/xu5767Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H32O2	F(000) = 360
Mr = 328.47	Dx = 1.151 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
a = 7.4250 (2) Å	Cell parameters from 3311 reflections
b = 10.5716 (3) Å	θ = 3.7–60.6°
c = 12.0747 (3) Å	µ = 0.55 mm−1
β = 90.124 (2)°	T = 180 K
V = 947.79 (4) Å3	Box, colourless
Z = 2	0.38 × 0.38 × 0.14 mm

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	2511 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2490 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.012
Detector resolution: 16.1978 pixels mm-1	θmax = 60.7°, θmin = 3.7°
ω scans	h = −7→8
Absorption correction: multi-scan Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (CrysAlis PRO, Agilent, 2012)	k = −11→11
Tmin = 0.860, Tmax = 1.000	l = −13→13
4370 measured reflections

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0433P)2 + 0.168P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.029	(Δ/σ)max < 0.001
wR(F2) = 0.075	Δρmax = 0.13 e Å−3
S = 1.04	Δρmin = −0.14 e Å−3
2511 reflections	Extinction correction: SHELXL2013 (Sheldrick, 2013), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
225 parameters	Extinction coefficient: 0.050 (2)
1 restraint	Absolute structure: Refined as an inversion twin.
Hydrogen site location: inferred from neighbouring sites	Absolute structure parameter: 0.0 (3)

Experimental. Absorption correction: Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (CrysAlis PRO; Agilent Technologies, 2012)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

	x	y	z	Uiso*/Ueq
C1	0.6487 (3)	0.6992 (2)	0.17276 (16)	0.0270 (5)
C2	0.4780 (3)	0.7203 (2)	0.13012 (17)	0.0283 (5)
C3	0.3461 (3)	0.7823 (2)	0.18816 (19)	0.0334 (5)
H3	0.2304	0.7948	0.1562	0.040*
C4	0.3833 (3)	0.8262 (2)	0.29347 (18)	0.0319 (5)
H4	0.2916	0.8682	0.3341	0.038*
C4A	0.5533 (3)	0.81000 (19)	0.34131 (17)	0.0244 (5)
C4B	0.5942 (3)	0.8675 (2)	0.45589 (18)	0.0258 (5)
C5	0.4239 (3)	0.8711 (3)	0.52884 (19)	0.0346 (6)
H5A	0.3376	0.9327	0.4972	0.041*
H5B	0.3659	0.7868	0.5276	0.041*
C6	0.4646 (3)	0.9074 (3)	0.6486 (2)	0.0406 (6)
H6A	0.5144	0.9942	0.6509	0.049*
H6B	0.3515	0.9067	0.6919	0.049*
C7	0.5980 (3)	0.8167 (3)	0.70024 (18)	0.0371 (6)
H7A	0.5427	0.7315	0.7033	0.045*
H7B	0.6222	0.8438	0.7773	0.045*
C8	0.7773 (3)	0.8075 (2)	0.63830 (18)	0.0338 (5)
C8A	0.7386 (3)	0.7834 (2)	0.51303 (17)	0.0275 (5)
H8A	0.6896	0.6954	0.5093	0.033*
C9	0.9073 (3)	0.7813 (3)	0.44192 (19)	0.0372 (6)
H9A	0.9521	0.8687	0.4322	0.045*
H9B	1.0022	0.7319	0.4801	0.045*
C10	0.8707 (3)	0.7233 (3)	0.32926 (18)	0.0366 (6)
H10A	0.9617	0.7561	0.2768	0.044*
H10B	0.8890	0.6307	0.3351	0.044*
C10A	0.6862 (3)	0.74630 (19)	0.28005 (17)	0.0261 (5)
C11	0.7945 (3)	0.6336 (2)	0.10479 (18)	0.0343 (6)
H11	0.8978	0.6181	0.1562	0.041*
C12	0.7413 (4)	0.5048 (3)	0.0572 (2)	0.0540 (8)
H12A	0.8501	0.4562	0.0400	0.081*
H12B	0.6704	0.5170	−0.0105	0.081*
H12C	0.6691	0.4585	0.1117	0.081*
C13	0.8634 (4)	0.7225 (3)	0.0150 (2)	0.0518 (7)
H13A	0.9103	0.7998	0.0492	0.078*
H13B	0.7644	0.7440	−0.0355	0.078*
H13C	0.9597	0.6807	−0.0266	0.078*
C14	0.6541 (4)	1.0050 (2)	0.4337 (2)	0.0433 (6)
H14A	0.5590	1.0497	0.3933	0.065*
H14B	0.7647	1.0047	0.3895	0.065*
H14C	0.6768	1.0478	0.5044	0.065*
C15	0.8902 (4)	0.9257 (3)	0.6616 (2)	0.0489 (7)
H15A	0.9251	0.9270	0.7399	0.073*
H15B	0.8193	1.0013	0.6444	0.073*
H15C	0.9986	0.9243	0.6154	0.073*
C16	0.8803 (4)	0.6933 (3)	0.6843 (2)	0.0561 (8)
H16A	0.8152	0.6154	0.6657	0.084*
H16B	0.8905	0.7008	0.7649	0.084*
H16C	1.0009	0.6905	0.6516	0.084*
C17	0.3222 (3)	0.5899 (2)	0.00169 (19)	0.0345 (6)
C18	0.3010 (4)	0.5659 (3)	−0.1197 (2)	0.0460 (7)
H18A	0.1878	0.5206	−0.1331	0.069*
H18B	0.4021	0.5146	−0.1461	0.069*
H18C	0.2991	0.6467	−0.1594	0.069*
O1	0.4419 (2)	0.68523 (16)	0.01943 (11)	0.0338 (4)
O2	0.2470 (2)	0.53449 (19)	0.07423 (14)	0.0491 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0302 (12)	0.0261 (11)	0.0248 (11)	0.0012 (10)	0.0028 (9)	0.0023 (9)
C2	0.0305 (12)	0.0316 (12)	0.0230 (10)	−0.0026 (10)	0.0004 (9)	0.0014 (9)
C3	0.0244 (12)	0.0444 (13)	0.0315 (12)	0.0021 (11)	−0.0022 (9)	0.0002 (10)
C4	0.0269 (12)	0.0355 (12)	0.0333 (12)	0.0060 (10)	0.0031 (9)	−0.0010 (10)
C4A	0.0256 (11)	0.0205 (10)	0.0271 (11)	0.0010 (9)	0.0026 (8)	0.0024 (9)
C4B	0.0262 (11)	0.0221 (10)	0.0290 (11)	0.0006 (9)	0.0022 (9)	−0.0022 (9)
C5	0.0302 (12)	0.0422 (13)	0.0314 (12)	0.0063 (11)	0.0022 (10)	−0.0072 (10)
C6	0.0327 (13)	0.0533 (17)	0.0357 (13)	0.0027 (12)	0.0065 (10)	−0.0129 (12)
C7	0.0413 (14)	0.0448 (14)	0.0253 (11)	−0.0082 (12)	0.0023 (10)	−0.0068 (11)
C8	0.0342 (12)	0.0386 (13)	0.0286 (11)	0.0002 (11)	−0.0037 (9)	−0.0071 (10)
C8A	0.0269 (11)	0.0271 (11)	0.0286 (11)	−0.0019 (10)	−0.0001 (9)	−0.0041 (9)
C9	0.0276 (12)	0.0497 (14)	0.0343 (13)	0.0040 (11)	−0.0011 (9)	−0.0077 (11)
C10	0.0280 (12)	0.0513 (15)	0.0305 (12)	0.0089 (11)	0.0005 (10)	−0.0047 (11)
C10A	0.0261 (11)	0.0259 (11)	0.0263 (11)	0.0000 (9)	0.0031 (9)	0.0028 (9)
C11	0.0322 (12)	0.0457 (14)	0.0251 (11)	0.0109 (11)	0.0018 (9)	−0.0012 (10)
C12	0.0587 (19)	0.0487 (17)	0.0546 (17)	0.0163 (14)	0.0060 (14)	−0.0166 (13)
C13	0.0399 (15)	0.0696 (19)	0.0460 (15)	0.0121 (14)	0.0175 (12)	0.0119 (14)
C14	0.0599 (17)	0.0281 (13)	0.0421 (14)	−0.0045 (12)	−0.0035 (12)	0.0017 (11)
C15	0.0363 (14)	0.0662 (18)	0.0441 (15)	−0.0116 (13)	−0.0023 (11)	−0.0189 (14)
C16	0.068 (2)	0.0664 (18)	0.0338 (13)	0.0231 (17)	−0.0133 (13)	−0.0045 (14)
C17	0.0352 (13)	0.0364 (13)	0.0319 (12)	0.0016 (11)	−0.0017 (10)	−0.0013 (10)
C18	0.0489 (16)	0.0560 (17)	0.0332 (13)	−0.0039 (13)	−0.0023 (11)	−0.0089 (12)
O1	0.0341 (9)	0.0432 (9)	0.0239 (8)	−0.0036 (8)	−0.0002 (6)	−0.0011 (7)
O2	0.0587 (12)	0.0514 (11)	0.0372 (9)	−0.0160 (10)	0.0039 (9)	−0.0001 (9)

C1—C2	1.385 (3)	C9—H9A	0.9900
C1—C10A	1.415 (3)	C9—H9B	0.9900
C1—C11	1.526 (3)	C10—C10A	1.512 (3)
C2—C3	1.372 (3)	C10—H10A	0.9900
C2—O1	1.412 (3)	C10—H10B	0.9900
C3—C4	1.381 (3)	C11—C13	1.524 (4)
C3—H3	0.9500	C11—C12	1.530 (4)
C4—C4A	1.398 (3)	C11—H11	1.0000
C4—H4	0.9500	C12—H12A	0.9800
C4A—C10A	1.406 (3)	C12—H12B	0.9800
C4A—C4B	1.541 (3)	C12—H12C	0.9800
C4B—C5	1.543 (3)	C13—H13A	0.9800
C4B—C14	1.544 (3)	C13—H13B	0.9800
C4B—C8A	1.553 (3)	C13—H13C	0.9800
C5—C6	1.526 (3)	C14—H14A	0.9800
C5—H5A	0.9900	C14—H14B	0.9800
C5—H5B	0.9900	C14—H14C	0.9800
C6—C7	1.512 (4)	C15—H15A	0.9800
C6—H6A	0.9900	C15—H15B	0.9800
C6—H6B	0.9900	C15—H15C	0.9800
C7—C8	1.532 (3)	C16—H16A	0.9800
C7—H7A	0.9900	C16—H16B	0.9800
C7—H7B	0.9900	C16—H16C	0.9800
C8—C15	1.530 (4)	C17—O2	1.193 (3)
C8—C16	1.533 (4)	C17—O1	1.361 (3)
C8—C8A	1.560 (3)	C17—C18	1.496 (3)
C8A—C9	1.520 (3)	C18—H18A	0.9800
C8A—H8A	1.0000	C18—H18B	0.9800
C9—C10	1.516 (3)	C18—H18C	0.9800
C2—C1—C10A	117.49 (18)	H9A—C9—H9B	108.0
C2—C1—C11	121.51 (18)	C10A—C10—C9	116.61 (19)
C10A—C1—C11	120.92 (19)	C10A—C10—H10A	108.1
C3—C2—C1	122.74 (18)	C9—C10—H10A	108.1
C3—C2—O1	118.32 (18)	C10A—C10—H10B	108.1
C1—C2—O1	118.77 (18)	C9—C10—H10B	108.1
C2—C3—C4	119.29 (19)	H10A—C10—H10B	107.3
C2—C3—H3	120.4	C4A—C10A—C1	120.89 (19)
C4—C3—H3	120.4	C4A—C10A—C10	120.43 (18)
C3—C4—C4A	121.18 (19)	C1—C10A—C10	118.65 (18)
C3—C4—H4	119.4	C13—C11—C1	110.0 (2)
C4A—C4—H4	119.4	C13—C11—C12	111.6 (2)
C4—C4A—C10A	118.38 (18)	C1—C11—C12	115.1 (2)
C4—C4A—C4B	119.92 (18)	C13—C11—H11	106.5
C10A—C4A—C4B	121.63 (18)	C1—C11—H11	106.5
C4A—C4B—C5	111.23 (17)	C12—C11—H11	106.5
C4A—C4B—C14	105.79 (18)	C11—C12—H12A	109.5
C5—C4B—C14	108.22 (19)	C11—C12—H12B	109.5
C4A—C4B—C8A	107.92 (17)	H12A—C12—H12B	109.5
C5—C4B—C8A	109.04 (17)	C11—C12—H12C	109.5
C14—C4B—C8A	114.6 (2)	H12A—C12—H12C	109.5
C6—C5—C4B	112.74 (18)	H12B—C12—H12C	109.5
C6—C5—H5A	109.0	C11—C13—H13A	109.5
C4B—C5—H5A	109.0	C11—C13—H13B	109.5
C6—C5—H5B	109.0	H13A—C13—H13B	109.5
C4B—C5—H5B	109.0	C11—C13—H13C	109.5
H5A—C5—H5B	107.8	H13A—C13—H13C	109.5
C7—C6—C5	111.0 (2)	H13B—C13—H13C	109.5
C7—C6—H6A	109.4	C4B—C14—H14A	109.5
C5—C6—H6A	109.4	C4B—C14—H14B	109.5
C7—C6—H6B	109.4	H14A—C14—H14B	109.5
C5—C6—H6B	109.4	C4B—C14—H14C	109.5
H6A—C6—H6B	108.0	H14A—C14—H14C	109.5
C6—C7—C8	114.08 (19)	H14B—C14—H14C	109.5
C6—C7—H7A	108.7	C8—C15—H15A	109.5
C8—C7—H7A	108.7	C8—C15—H15B	109.5
C6—C7—H7B	108.7	H15A—C15—H15B	109.5
C8—C7—H7B	108.7	C8—C15—H15C	109.5
H7A—C7—H7B	107.6	H15A—C15—H15C	109.5
C15—C8—C7	109.6 (2)	H15B—C15—H15C	109.5
C15—C8—C16	107.7 (2)	C8—C16—H16A	109.5
C7—C8—C16	107.9 (2)	C8—C16—H16B	109.5
C15—C8—C8A	114.3 (2)	H16A—C16—H16B	109.5
C7—C8—C8A	109.00 (17)	C8—C16—H16C	109.5
C16—C8—C8A	108.25 (19)	H16A—C16—H16C	109.5
C9—C8A—C4B	109.05 (18)	H16B—C16—H16C	109.5
C9—C8A—C8	113.59 (17)	O2—C17—O1	123.7 (2)
C4B—C8A—C8	117.57 (17)	O2—C17—C18	126.0 (2)
C9—C8A—H8A	105.2	O1—C17—C18	110.3 (2)
C4B—C8A—H8A	105.2	C17—C18—H18A	109.5
C8—C8A—H8A	105.2	C17—C18—H18B	109.5
C10—C9—C8A	111.51 (18)	H18A—C18—H18B	109.5
C10—C9—H9A	109.3	C17—C18—H18C	109.5
C8A—C9—H9A	109.3	H18A—C18—H18C	109.5
C10—C9—H9B	109.3	H18B—C18—H18C	109.5
C8A—C9—H9B	109.3	C17—O1—C2	117.79 (16)